We study efficiency of autoionization and recombination transitions for europium in CaxCd1-xF2host lattice depending on the energy level position of Eu2+4f65d1(e) excited states in respect to the conduction band (CB) states. From photoluminescence (PL) and absorption measurements we conclude that for x in the range of 1 - 0.65 thermalization within the 4f65d1(e) multiplet is faster than the appropriate autoionization transition.For x > 0.65, when all the excited 4f65d1states are degenerate with the CB autoionization is immediate, Eu2+intra-ion emission is quenched and a new Eu-related emission appears, which we tentatively assign to a radiative capture emission of hot nonequilibrium electrons.